Insoluble azo dyes



' Patented Dec. 19, 1944 INSOLUBLEAZO nYEs 7 Peter F. Gross, Woodstown, N. 1., assignor to E. I.

du Pont de Nemours & Company, Wilmington Del.. a corporation of Delaware No Drawing. Application August 30, 1941,

Serial No. 409,002: 1

' I '9 Claims.

.This invention relates to new insoluble azo dyes, to dyeings produced with the dyes and to processes of manufacturing the same, and especially to dyes which are represented by the formula wherein C5I-I4 is the residue of pyridine, -Ph, is the residue of a phenylene group which is devoid of water solubilizing groups but may be substituted by other groups, and A is the residue of an ice color coupling component.

Heretofore it has been proposed to provide blue dyes of somewhat similar structure in which a furoylor thenoyl-phenylene-diamine was diazotized and coupled with an arylide of beta hydroxy naphthoic acid. However, these furoyl and thenoyl dyes were not entirely satisfactory in that their light fastness, resistanceto chlorine and dischargeability were not as good as were required in high standards of dyeing. It was desirable to provide new dyes in blue and other shades which hadbetter characteristics in the respects referred to.

It is amongthe objects of the present invention to provide new insoluble azo dyes which are represented, .in general-by the formula C5H4N-CONH-PhN=NA in which the symbols have the significance hereinabove described. Another object of the invention is to provide dyes in shades of blue to red which have satisfactory dischargeability and fastness to light I and chlorine. Other objects of the invention will be apparent from the following description.

The objects of the invention are attained by first providing primary arylamines which are represented by the formula C5HI4N:CONH- PhNH2 wherein C5H4N--CO is the residue of a pyridine carboxylic acid and -,HIN-PhNI-I2 isthe residue of a phenylene-diamine which is devoid of free carboxy and sulfonic acid groups but which can be substituted by other groups which do not produce water solubility. This pyridinecarbonyl diphenylamine is then diazotized and coupled by suitable means with an ice color coupling component to form a dyeing n.dyeable fibrous material or a. pigment, as the case may be. i

The invention will be more fully set forth in the following more detailed description which includes examples that are given as illustrative embodiments of the invention and not as limitations, thereof. Parts are expressed in parts by weight unless otherwise noted.

' EXAMPLE 1 (a) Preparation of 4-picoli nylaminoe2j diethoxy nitro-benzene A mixture of 123 parts picolinic acid, 113 parts of 4-nitro-2,5-diethoxy-aniline, 121 parts dimethyl-aniline and 1200 parts toluene was heated to G. Then 55 parts of phosphorus-trichloride-was added over a period of 20-30 minutes. The temperature was held at 80-90 C.

for one hour and was then raised to the boiling point of the mixture where it was held for 12 hours longer. When the reaction was completed, steam was-blown into the mixture until all steam-volatile material had been distilled off. The residue was filtered and the solid product waswa'shed thoroughly with hot water and dried. There was obtained 114 parts of crude product. The crude product was purified by recrystallization from the ethyl ether of ethylene' glycol, yielding 4-picolinyl-amino-2,5-diethoxy-nitro-benzene which was a bright yellow crystalline material melting at 172 C.

(1)) Preparation of 4-plicoZinylamino-2j- I v diethoxy -aniline .A mixture of .122 parts of =4-picolinylamino- 2,5-diethoxy-nitro-benzene, 6 I parts reduced nickel catalyst,rand 375 parts toluene was placed in aclosed autoclave and heated at 100 C. under a pressure of, ydrogen at 400-500 pounds gauge. When absorption of hydrogen was completed, the hot solution was filtered to remove the catalyst and a yield of 70 parts of product crystallizedout as a dark' yellow solid upon Preparation of 4-picoZinylamino-2,5-dimethowy aniline A mixture of 72.5 parts of sodium picolinate,

parts of 2,5-dimethoxy-aniline and 400 parts of toluene was treated with 34 parts of phosphorus tri-chloride. The temperature was raised to the boilin'g 'point and the mixture re- The toluene solution was added slowly to 420 parts of nitric acid. The mixture was held at 50-60 C. with good agitation during the addition and it was then heated to and helcLat;v 75 C. for 15 to minutes. The toluene was then removed by distillation and the solid prod-.

uct was filtered ofi, washed with methyl alcohol and dried, giving 136 parts of the nitIOLCOm'F- pound. V

The nitro compound was placedjimanauto;

pyridine was heated at 95-100 for 2 hours and then poured into 600 parts of cold water. After standing overnight, the crystalline product, a bright yellow material, was filtered and washed with water until the odor of pyridine could no longer be detected, and then dried. A yield of 64 parts of 4-nicotinylamino-2,5-diethoxy-nitrobenzene having1a.melting pointi of 127 C. was obtained.

(11) Preparation of 4-mcotinylamino-2,5-dieth omy-aniline A..mixtur e. of 16.6, parts of 4-nicotinylamino- 2,5;diethoxy -nitro-benzene, 150 parts methyl alclave together with 600 parts of*toluene, 3pa-rts. 157 conehanlafimartsjofireduced nickel catalyst was of calcium carbonate and 13 parts of reduced nickel catalyst. The mixture was h'eated -2a t100 C. and under a pressure of hydrogen of roe-500:

pounds gauge until hydrogenation wasa. come.

pleted. The catalyst was removed by filtering the 20 hot mixture and the toluenee solution wasscon centrated at atmospheric pressureto'acvolume oi- 200-400 parts. The crystalline product of 4- picolinylamino 2,5 dimethoxy aniline was filteredofi; washed with methyl alcoholzand dried, yielding 106 parts-of-the product.

v EXAMPLEABL I (a) Preparation of Z-m'tro-hmethoxy;5::pic0lin:

v ylamino -tolue1 te A-mixtu're 017 art i 9diumtp colinate.;75.::

parts of..cresidine, 400 parts toluene and .34 parts;

phosphorus tri-chloride. was refluxed T0133 hours; The toluene was removed by steam distillation;,,

placed in a closed autoclave and heated at 100 C: undera pressure of hydrogen of 400-500 pounds gauge. After the absorption of hydrogen wasgcompleted, the mixture was removed from the autoclave and filtered while still hot. The filtrate was evaporated to y-ield the'light-colored, crystalline product? consisting of 4-nicotinyl amino-2,5diethoxy-aniline;

25, EXAMPLE 5 (a) Prepaz mtion.- of" 4+isomicotinylamino-Zj-cliethoxy-nitro-benaene -aniline, .14: Partslisoenicotinyl-achlorides and; as;

and the duei s lte eda driedigivingilzaa; -with ;water;xzandlr.driedn Ac yie1d-1ofi21;5 parts-voila:

parts of condensation product Was,;--dis solved in 300. partsoit lufine and-,jthe;;solntion; was filtered from a small amOunliiofi-zinsolublec impurity.v The-solutionwasthen runslowly intoe crude 4Fiso=nicotinyl1aminoe2;5+diethoxyenitroe-- benzeneswaspbtained. Thisiwasireedcfromicone taminationtwith:unreacted: 4-1nitroe2,5diethoxy+ aniline ;;by;. treatment awithmitrous lacidcsufiieient 4:

420 parts of 15% ,nitricagid vigproumagitationyl completely toidiazotizesthe unreacted amindbody;

s n a ned and he t mp rature waszhcldc t he il n po :of he mixturexsnt saam during the additionamt then;,-fon :,minutese more.- Thereafter; the, toluene wasg remfl edgby steam i l tion u helmater al; ppeaLed:zioti-4 to be completely nitrated, The material was, separated-from the-waterlayer, and redissolved in 300 parts toluene; This solution was run as beforeat the, boilcinto 310;parts:of: 20% :nitric acid.

The mixture jwas cooled-filtered and-dried yield-b ing 58 parts of,g,2enitro=4+methoxy=5epicolinylaa amino toluene which; .was...a lcrystallineaproductr ExAMPLii 4 (a) Preparation of. 4 hicotinylamino-2,,5 di fih omy-nitrobenzene,

Amixture-oflf 2 partspf 4- nitrol-2,5ediethoxy-r filtering: andgwashingafreen-ifrom ;di-azo:;and ifI'Oma tiidc Therproduct isrepnesented. .byatheiormula;

' (bi Preparation of'4-isonicotinyl amin-o-zfidi ethomyaniline A=;mixture-,ot 1QParts.ofiA-dsomicotinyleaminm 2.5:diethoxy-nitro-benzene, 7,100."; parts; of. :methyl-z 5 alcohol-and 2 parts .of::reduced -nickelcatalyst was placed :in; a closed ;,a.utoclav rand heated-:at; 100i; C. under a pressure of hydrogen;-v of; 4001500: pounds gauge. After the absorption of hydrogen was complete;- the 'mixtur-e'was filtered hot to redo move spent catalyst. The-filtrate wasevaporated,

to yield the crystalline 4-,iso.-nicotinylamino;-2,5,,- diethoxy anilinel EiIAMPLE .6':

(a); Preparation, of, 3 picolinylaminoenittoe 1 benzene n n 42;Part .micotinylphlgride: and pane 5a andt'atheicrudexproductiwas :filtered' ofi' frem the residue. This product still contained unreacted m-nitraniline, which was removed by treatment of an aqueous slurry of the material with hydrochloric acid and sodium nitrite, filtering; and washing fre from acid and diazotized m-n'iftraniline. The dried product consisted of '75 partsof 3-picolinylamino-nitro-benzene having a melting point of 167 C.

(b) Preparation of 3-picolinylamino-am'line.

A mixture of 60.8 parts of 3-picolinylaminonitrobenzene, 300 parts of methyl alcohol and- 6 parts of reduced nickel catalyst was placed in an autoclave and heated-at 100, Crunder a pressure of hydrogen of 400-500 pounds gauge until the absorption .of hydrogen was completed. The charge was then removed from the autoclave and filtered hot to remove the catalyst.

The filtrate was evaporated to dryness, giving a yield of 49 parts of 3-picolinylamino-aniline containing 19.7%- nitrogen. The theoretical con- 7 toluene A mixture of 463 parts of 2-picolinyl-amino- 4-nitro-toluene, 4 parts nickel catalyst and 200 tent of nitrogen in 3-picolinylamino-aniline is EXAMPLE 7 r (a) Preparation of 4-m'colinylamino-3-chloro- Y nitrobenzene A mixture of '75 parts of. sodium picolinate, 89 parts of2-chloro-4-nitro-aniline and 1000 parts toluene was heated to 70 C. and 34.2 parts of phosphorus tr'i-chloride was added over a (b) Preparation of 4-picdli1'tylami1tO-3 chloroaniline A mixture of 55.4 parts of 4-picolinylamino-3- chloro-nitrobenzene, 350 parts of methyl alcohol and 5 parts reduced nickel \catalyst was heated in an autoclave at 100 C. under a pressur 'of hydrogen of 400-500 pounds pressure until the hydrogenation was completed. The charge was filtered hot to. remove the catalyst and the illtrate was evaporated to dryness, giving 36.5 parts of 4-picolinylamino-3-chloro-aniline analyzing 16.63% nitrogen and 14.63% chlorine. The theoretical content of nitrogen/and chlorine in this product is 16.97% nitrogen and 14.34% chlorine. u EXAMPLES v I (a)- Preparation of- 2-picoZinylamino-4-nitro- P toluene A mixture of 75 parts of sodium picolinate, 63 parts of 4-nitro-2-amino-toluene and 1000 parts toluene was warmed to 70 Cland 28 parts phosphorus tri-ohloride were added to the mixture over a period of 10-15 minutes. After the mixture had been heated to the boiling point and refluxed for 8 hours, the toluene was distilled out with steam and the residue [was cooled,

filtered off and dried, giving 89 parts of crude parts methyl alcohol was hydrogenated in a closed autoclave at C. under a pressure of hydrogen of 400-500 pounds gauge until the nitro was reduced to amino. The catalyst was removed by filtering" the .hotv solution and the filtrate was evaporated to a volume of about 60 parts cooled, and filtered. The crystalline product.'- consistin of 2- picolinylamino-4-aminotoluene weighed 33.5 parts when dry. Its melting point was, 145C. and it contained 18.25% nitrogen. The theoretical content of nitrogen in.

C13H13ON3 is 18.51% c 7 A P E 9 ,(a) Preparation ofv 2-pic0linylamino-5-nitroanisole I Amixture of '75 parts of sodium picolinate, 84 parts 5-nitro-2-amino-anisole and. 1000. parts toluenewas warmed to 70 C. and 34.2 parts of phosphorus tri-chloride was added'over a period of 10-to 15 minutes. :After heating the mixture to boiling. and refluxing for 8 hours, the. toluene was distilled out with steam and the residue was cooled, filteredanddried, yielding parts of crude product. The crude product was purified by recrystallization successively .from the ethyl.

ether of ethylene glycol, to1uene,-and .ethyl alcohol." The purified product consisting of 2-picolinylamino-5-nitro-anisole melted at 209 C. and contained 15.00% 'nitrogen,56.8l% carbon and 4.35% hydrogen. The theoretical content of nitrogen, carbon and hydrogen inC13H1'1O4N3 is 15.38% N, 57.14% C, and 4.07% H.

(b) Preparation of Z-zn'colinylamino-5-aminoanisole A mixture or 20 parts 'of 2-picolinylam'ino 5- nitro-anisole, 2 parts reducednickel' catalyst and 200 parts methyl alcohol was placed in a closed autoclave and heated at 100? under a pressure of hydrogen of 500-600 pounds gauge. The catalyst was remo'ved'by filtering the hot solution; The filtrate was evaporated to a volume ofabout 60 parts and cooled. A crystalline. product consisting of 8 partsof 2-picolinylar'nino-5- amino-anisole and melting at 134 C.'was filtered oil anddried. An additional quantity of less pure material was recovered from the filtrate.

ExAMPLE 10 ter at F. Then 97 parts of hydrochloric acid -(32.Tw.) was added and mixed in thoroughly. Water and ice sufficient to bring the volume to 4000 parts and-the temperature to 50 F. were added, followed by a solution containing 23.2 parts of sodium nitrite added over a period of 5 to 10 minutes. The diazo solution was allowed to stand for 30 minutes at,50-55 F., diluted to a volume of 30,000 parts and then buffered by adding 346 parts of sodium acetate.

When the development of the color was complete, the piece was rinsed, soaped at-the boil, rinsed again and dried. A bright blue dyeing, having very good fastness to light, washing, chlorine and power laundry was obtained.

(5) Preparation o 2-picolinylamino-4-a'mino- -'Ihe dye isrepresented bythe formula The fastness of the dyeing both to light and to chlorine was superior to' that of the dyeing made by coupling diazotized 4-furoylamino-2,5'- diethoxy-aniline with N-(2'-hydroxy-3'-naphthoyl) -aniline on cotton and its fastness to chlo rine was very much superior to that of the dyeing made by coupling 4-alpha-thienoyl-amino- 2,5-diethoxy aniline with N-(2'-hydroxy-.-3"- naphthoyll-aniline on cotton.

Exsiurrn 11 A piece of cotton piecegoods was impregnated in the usual manner with N-(2'-hydroxy-3'- naphthoyD-aniline. A diazo bath containing 100 parts of diazotized 4-iso-nicotinyl-amino- 2,5-diethoxy-ani1ine' was prepared in the manner described in Example 10 except that 4-iso-nico-' tinylamino-zfi-diethoxy aniline was used as the amino base instead of 4-picolinylamino-2g5-diethoxy aniline. xThe dyeing was developed by applying the diazo solution to the impregnated goods A blue dyeing was produced by the formation of the azo dye represented by the following formula.

' on. -NHG OCzHy The dye possessed good fastness to light, chlorine, and washing.

EXAMPLE 12 A piece of cotton goods, impregnated in the usual manner with N-(2'-hydroxy-3'-naphthoyD-o-toluidine, was developed in a diazo bathprepared as described in Example from I 4-picolinylamino-2,5-diethoxy-aniline. Abright greenish blue dyeing of very good fastness to light, washing, chlorine and power laundry was obtained. The dye is represented by the formula OCZHS ()H (BO-NH assumes.

EXAMPLE 1.4

A piece of cotton goods, impregnated in the usual manner with N-(2'-hydroxy-3-naphthoyl)-1 amino-naphthalene, was developed in adiazo bath prepared as described in Example 10 from 4-picolinylamino-2;5-diethoxy-aniline. A greenish blue dyeing of good fastness to light, crocking, chlorine and washing was obtained.

way with 'N-(2-hydroxy-3'-naphthoyl) -p-anisidine, was developed in a diazo bath prepared as described in Example 10 from l-picolinylamino- 2,5-diethoxy-aniline. A navy blue dyeing was obtained which had. good. fastness to light, chlorine and washing. The dye is represented by the formula OCH OHOONH' 00H: 2 i 1 ii \N MHQM V CaHs EXAMPLElG A piece of cotton goods, impregnated in the usual way with N-(2-hydroxy-3 -naphthoyl) -2- amino-naphthalene, was developed in a diazo bath prepared as described in Example 10 from 4-picolinylamino-2,5-diethoxy-aniline. A deep blue dyeing was obtained which had good fastness 'to washing, chlorine and light. The dye is represented by the formula G I on 0 ONE EXAMPLE 17 A diazo solution wa prepared by dissolving 161.5 parts of 4-picolinylamino-2,5-diethoxy-aniline in a mixture consisting of 1920 parts of ice water and 311 parts of 22% hydrochloric acid and then slowly adding 124.2 parts of 30% sodium nitrite solution. The diazo solution was clarifled and slowly added over a period of 1 hour to a solution containing 91 parts of sodium pipecolinate, 299 parts of sodium carbonate and 2300 parts of water. After the dark colored solution had been allowed to stand for'four hours at room temperature, it was filtered to remove a small amount of insoluble impurity. Upon adding two thousand parts of a 30% caustic soda solution, a product separated out in the form of a dark colored viscous layer. The viscous product was removed and dried at 40 to 50 C. under diminished pressure. The dried product consisted of 259 parts of a dark brown solid which was 66.2%

pure. This diazoimino compound is represented by the formula CHr-CHr I CH:

CHg-C OONa .A printing paste was made by mixing Thediaz'oimino compound prepared as described above N-(2'-hydroxy- 3-naphthoyl) -o-toluidine 1.2 Ethylene glycol-mono-ethyl ether 4.0 35% sodium hydroxide solution 4.0

Water Starch-tragacanth thickener 70.0

A piece of cotton piece goods was printed from an engraved copper roll with the above paste. The printed fabric was placed for four minutes at 100 C. in an atmosphere of saturated steam containing the vapors of acetic and formic acids.

The printed pattern developed to a greenish blue dyeing due to the formation On the fiber of the dye of'the formula given in Example 12. The printed cloth was then rinsed, soaped, rinsed again, and dried. The printed pattern showed good fastness to washing, chlorine and light.

EXAMPLE 18 A diazo bath was prepared from 85 parts of 2-amino-4-methoxy-5-picolinylamino-toluene, 97

aniline with. 10 parts. of ethyl alcohol, adding 5 parts of 32% sodium hydroxide and, then diluting with 500 parts of water. An equivalent quantity of diazotized 4-picolinylamino-2,5-dieth0Xy-aniline,v prepared as described in Example 10 was added to the solution of the aniline. An insoluble blue-black pigment was formed. This was filtered ofi, washed and dried. The pigment was soluble in concentrated sulfuric acid to a bluegreen solution.

. :1 EXAMPLE 21 solution of acetoacetyl-pephenetidine, was.

prepared by stirring 10 parts. of this compound with 10 partsof ethyl alcohol, adding 7 parts of 32% sodium hydroxide solution and then diluting with 500 parts of water. An equivalent quantity of diazotized 4;-picoliny1amino-'2,5-diethoxy-aniline, prepared asdescribed in Example 10, was

added to the solution of the acetoacetyl-p-phenetidine. An insoluble yellowish-brown pigment was precipitated. It was filtered, washed and dried. The driedproduct was .a dark red-brown powder which was soluble in concentrated sulfuric acid giving a wine-colored solution.

ExAMPLr: 22

A' piece of cotton piece goods, impregnated-in the usual way with N-(2'-hydroxy-3f naphthoy1) aniline, was developed in a diazo bath made by the'r'nethod described in Example 10 from 71 parts of 3+pico1inylamino-ani1ine and by using the same relative quantities of icew'ater,' acid, nitrite and parts hydrochloric acid, (32 Tw.), 23.2 parts of. 1

'sodium nitrite and 346 parts of sodium acetate,

using the same temperatures, times and quantities of water as were used in Example 10. 1 a

' A piece of cotton piece goods, impregnated'in the usual way with N-(2'--hydroxy-3'-naph thoyll-aniline, was developed in, this bath and then rinsed, soaped, rinsed againand dried. A red-violet dyeing having good fastness to light, chlorine, washing and cracking was obtained. The dye is represented by the formula EXAMPLE 19 A piece of cotton piece goods, impregnated in the usual way with N-(2'-'hydro'xy-3-naphthoyl)-1-amino-naphthalene, was developed in a diazo hath made by the method described in example 10 from 91 parts of 4-picolinyl-amino-2,5- dimethoxy-raniline by using the same quantities of acid, ice water, nitrite and bufierandthesame times and temperatures used in Example 10. A

reddish blue dyeing of good fastness to washing, light, chlorine and crocking was obtained. The dye is represented by the formula m (M31513 OH. oo H LOO-NHQI E 1 summer) 0 A solution of N-(2'vhydroxy-3-naphthoyl)e aniline was prepared byystirring. 10 partsof the 'ness to crocking and rubbing was obtained.

buffer "and the same times and temperatures specified in Example 10.- A bluish-red dyeing of good general fastness properties, particularly fast- The dye is represented by the formula 0 EXAMPLE 23 OHACONHVOI "EXAMPLE 24=- A piece of cotton piece goods,impregnated in the usual way with N- (2'.-hydroxy -3'-naphthoyl) 0 aniline, wasdeveloped in a diazo bath made from parts of Z-picQlinyIammo- I-anfino toluene by using the same relativefquantities of ice Water, ,acid, nitrite and bufferand the same times and ,temperatures as those specified in Example 10.

.7.5 ;A' 'd yeing of good fastness properties, particularly to crocking and-light was obtained." The dye is represented by the formula; ,j

abovefuroylamino typedyestuif and also to that of the dyestufi made by coupling diazoti'zed 4- alpha-thenoyl-amino-2,5-diethoxy-ani1ine to N- (2'-hydroxy-3'-naphthoy1) aniline.

The following are other illustrations of the invention. In these examples dyeings were made by padding pieces of cotton goods with the indicated coupling components and then developing with the indicated diazo components in a manner'similar to the methods described in the foregoing examples. The shades of the resulting dyeings areindicated in the column entitled, Shade. AS compared to dyeingsproduced by analogous combinations with similar combinations of 4-furoylamino-anilines and. 4-thienoy1- amino-anilines, the combinations shown in the table had better dischargeability, light and chlorine fastness.

washing, chlorine, power laundry and light was obtained. The dye is represented by the formula (\H OH CONHQ N CONH CHIO,

r 7 Exam '2'6 ,r

A piece of cotton piece goods, impregnatedin the usual manner with N ('2"-hydroxy-3"-'naphthoyl) -aniline,. was -developed in a 'diazo hath madeup" from 100? partst'ot 4-nicotinyI'amino-2,5.- diethoxy-aniline *by'iusing: the same number of parts of ice water, acidonitrite and butter and the same times and temperatures as those specified in Example 10. A green-blue dyeing was obtained which is represented by the following formula oolm on (130N136 dischar'geability was superionboth to that of the Any of the indicated 'oombinationsoan be coupled in substance to produce pigments: having shades whichare somewhat similar to th'e'develope'd' dyeings and any of the combinations "can be applied to textile fabrics by padding or 'by printing processes as indicated hereinbefore. By the methods described, either the 2 3- or 4- pyridine carboxylic acid can be used to make the amino bases and either acid can be reacted with any 3-nitroor a. 4-nitro-aniline of the kinds indicated to produce nitro compounds represent ed by the general formula wherein X is from the group consisting of hydrogem'alkyl having 1 to 3 carbons, the-corresponding alko'xy groups, 'p'henyl, 'phenoxy. ch10- ro and bromo; and-n is an integer not greater than 2'. All of these nitro compounds can then be reduced to form the-correspondingprimary arylamines which are used as amino bases in making the. dyes.

As illustrative'of the many nitro-aniline which can be reacted. with the pi'colinic, nicotinic or isonicotinic acid to produce such nitro-pyridlnyh amino compounds of' the benzeneseries in addition to those shown in foregoing examples are mentioned 2-nitro-4-amino-5-chloro-toluene, 3- bromo-4-nitroani1ine, z-amino-s-nitro-diphenylether, 4-nitr'o-2,5-di-iso propoxy aniline, 2-nitro-e-amino-fi n-propoxy toluene, 2.-'nitro-'4- -asemccs hydrogenation catalyst can be used. ,The tem- 10 'perature and pressure of hydrogenation may be considerably varied. 'Temperatures of -.about 50 to about 200- C. and pressures of about 200 to about 1000 pounds gauge are suitable. More or less inert solvent can be used besides the proportions enumerated. Specific illustrations and other inert solvents besides toluene or methyl alcohol can be used By inert organic solvent is meant any organic solvent in which the nitro amino-5-picolinylamino-4-iso-propyl-toluene and 2-amino-4-chloro-5-picolinyl-amino-toluene.

Any ice color coupling component which is devoid of solubilizing groups, such as carboxyl and sulfonic acid can be used as the coupling com ponent to make the dyes of the invention, such as the arylamides of ortho hydroxy aryl carboxylic acids, phenolic coupling components and the arylamides of beta-keto carboxylic acids. As

illustrations of ice color coupling components arev mentioned the arylamides of 2-hydroxy-3-naphthoic acid, 2 hydroxy carbazole 3-carboxylic acid, 2-hydroxy-diphenylene-oxide-3-carboxy1ic acid, Z-hydroXy-anthracene-3-carboxylic acid, 7- hydroxy alpha naphthocarbazole-G carboxylic acid, terephthaloloyl-bis-acetic acid, aceto-acetic acid and benzoyl-acetic acid in which the arylamide groups are the residues of aniline, the toluidines, the xylidines, alkoxy-and aryloxy-anilines, halo and nitro-anilines, halogenated toluidines, halogenated xylidines, halogenated alkoxyand aryloxy-anilines, dianisidine, tolidine, alphaand beta-naphthylamine. Other such components are alphaand beta-naphthol and derivatives thereof, such as those which are substituted in the 5-, 6-, 7- or 8-positions by bromine, chlorine, amino, alkyl and alkoxy containing 1 to 6 carbons.

The developed dyeings, such as dyeings on textile fibers are made in accordance. with the invention by impregnating the material to be dyed with the coupling component, as by applying a suitable solution of the coupling component whereby the coupling component is aflixedly held by the fiber and then applying a 'diazo solutionfrom one of the new aminobases to attain development; by impregnating with the coupling component, printing with a printing paste containing a diazo salt of the arylamine or by converting the diazotized arylamine to a derivative thereof which is stable and non-reactive toward mula the coupling "component in alkaline medium, ap-

plying to the material to be dyed an alkaline composition containing the diazo derivative and the coupling component, such as a printing paste and then acidifying to effect development.

The new dyes are represented by the formula wherein C5H4N-- CO is the residue of the group consisting of a 2-, 3- or 4-pyridine 'carboxylic acid; the nucleus 'is'the residue of adiamine 'in which X is from to 3 carbons, the corresponding alkoxy groups,

phenyl, phenoxy, and halogen. The new dyes produce dyeings on suitable dyeable fibers in a variety of shades of yellows, blues and reds which have unusually good dischargeability, fastness to chlorine and fastness to light. Other fastness properties commonly required in satisfactory dyeings are good. The dischargeability, fastness to chlorine and fastness to light of the dyeings made in accordance with the invention are far superior to dyes of similar structure which differ from the new dyes in that thediazo component is an amino-furoylaminoor an thenoylamino compound of the benzene series.

The preferred class of arylamines are pyridinecarbonyl-amides of the formula and especially those wherein R is from the group consisting of hydrogen, methyl, methoxy, ethoxy and chloro. The dyes made by diazotizing the amides of this class and coupling with an arylide of 2,3-hydroxy-naphthoic acid have the best general properties together with the improvement in dischargeability, chlorine fastness and light fastness.

From the foregoing disclosure it will be recognized that the invention is susceptible of modification without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to the specific illustrations thereof herein set forth.

I claim:

1. An insoluble azo in which C5H4N-CO- is a residue of a pyridine carboxylic acid; X is from a. group consisting of hydrogen, alkyl having 1 to 3 carbons, the corresponding alkoxy groups, phenyl, phenoxy and halogen; n is 1 to 2; and A represents the residue of an ice color coupling component.

dye represented by the for- 2. Aninsoluble azo dye representedbythe formula wherein X is from a group consisting of hydrogen, alkyl having 1 to 3 carbons, the corresponding alkoxy groups, phenyl, phenoxy and halogen; n is 1 to 2; and A represents the residue of an ice color coupling component.

, 3. Aninsoluble azo dye represented by the formula (SCQH); wherein A. represents the residue of an arylide of 2,3-hydroxy-naphthoic acid.

4. Aninsoluble azo dye representedby the form-ula O CH;

OCO-HNQNT-N-A N wherein A represents the residue of an arylide ,of 2,3Y-h'ydroxy-naphthoic' acid.

5. An insoluble a-zo-dye represented by the formula.

wherein A represents the residue of an arylide of 2,3-hydroxy-naphthoic acid.

6. Textile fiber dyed with a dye of claim 1.

7-2 The process which comprises diazotizing a primary amine represented by the formula wherein C5H4N is the residue of pyridine; X is from a; group consisting of hydrogen, alkyl having 1 to 3 carbons, the corresponding alkoxy groups, phenyl-phenoxy and halogen and n is an integer not greater than 2'; and coupling with I Certificate of Correction Patent No. 2,365,265. December 19, 1944. PETER F. GROSS It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 1, first column, line 8, for C H read O;H N; page 5, first column, lines 3 to 9 inclusive, for that portion of the formula reading CHr- HI CHr-CH:\

CHr-CHI (JR-CH1 OONa COM:

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oifice.

Signed and sealed this 15th day of May, A. D. 1945.

[SEAL] LESLIE FRAZER,

Acting Commissioner of Patents. 

